EP2675876A1 - Schmiermittel mit guter tbn-retention - Google Patents
Schmiermittel mit guter tbn-retentionInfo
- Publication number
- EP2675876A1 EP2675876A1 EP12705222.3A EP12705222A EP2675876A1 EP 2675876 A1 EP2675876 A1 EP 2675876A1 EP 12705222 A EP12705222 A EP 12705222A EP 2675876 A1 EP2675876 A1 EP 2675876A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dispersant
- tbn
- lubricant
- lubricant composition
- tan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000314 lubricant Substances 0.000 title claims abstract description 74
- 230000014759 maintenance of location Effects 0.000 title claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 97
- 239000003599 detergent Substances 0.000 claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 claims abstract description 59
- 239000002184 metal Substances 0.000 claims abstract description 59
- 239000002253 acid Chemical group 0.000 claims abstract description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 23
- 239000003921 oil Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 24
- -1 succinic acid, ester Chemical class 0.000 claims description 24
- 230000001050 lubricating effect Effects 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 238000002485 combustion reaction Methods 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 8
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 150000003949 imides Chemical class 0.000 claims description 6
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 230000000994 depressogenic effect Effects 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 41
- 239000000463 material Substances 0.000 description 25
- 125000001183 hydrocarbyl group Chemical group 0.000 description 24
- 230000002378 acidificating effect Effects 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 15
- 125000001424 substituent group Chemical group 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 238000006386 neutralization reaction Methods 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 150000008064 anhydrides Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 7
- 229920002367 Polyisobutene Polymers 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000002199 base oil Substances 0.000 description 5
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 3
- 229960001860 salicylate Drugs 0.000 description 3
- 229960002317 succinimide Drugs 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000010689 synthetic lubricating oil Substances 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000013020 final formulation Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000010688 mineral lubricating oil Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 150000003870 salicylic acids Chemical class 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 150000003892 tartrate salts Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 1
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical group COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000007065 Kolbe-Schmitt synthesis reaction Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical class C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- GLOYGJPNNKTDIG-UHFFFAOYSA-N SC=1N=NSC=1S Chemical class SC=1N=NSC=1S GLOYGJPNNKTDIG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- SNCZNSNPXMPCGN-UHFFFAOYSA-N butanediamide Chemical compound NC(=O)CCC(N)=O SNCZNSNPXMPCGN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Definitions
- the disclosed technology relates to a lubricant, suitable for use in an internal combustion engine, which containing a metal-containing detergent which provides basicity to the lubricant.
- a defined dispersant is present, leading to superior retention of the basicity (TBN, ASTM D 974) during use of the lubricant.
- Lubrication of internal combustion engines has been a practice for many decades, yet continual improvement in lubricant technology is ongoing as new engines and new standards have been developed.
- Formulations directed to passenger car engines for instance, must address limits placed on sulfated ash, phosphorus, and sulfur content (“SAPS"), and restrictions in these components often lead to upper limits on the amount of metal-containing detergent that can be included in the lubricant.
- SAPS sulfated ash, phosphorus, and sulfur content
- One of the benefits that metal-containing detergents provide to the lubricant is basicity (measurable as TBN), which is available for various functions, including neutralization of acidic byproducts of combustion.
- TBN basicity
- some engine tests specify a minimum TBN level remaining at the end of the test.
- TBN retention has become an important parame- ter in design and selection of engine lubricants.
- Good TBN retention is associated with the ability of a lubricant to protect the engine from corrosive wear and maintaining that protection over an extended period of time.
- the disclosed technology therefore, solves the problem of providing good TBN retention (and associated benefits) by selection of a suitable dispersant, as described herein.
- the desirable dispersants typically have a high total acid number (TAN).
- the disclosed technology provides a lubricant composition
- a lubricant composition comprising: (a) an oil of lubricating viscosity; (b) at least one metal-containing detergent in an amount to provide at least 2 TBN to the lubricant; (c) a dispersant comprising an oleophilic portion comprising at least 40 carbon atoms and an acid-bearing portion, characterized in having a TAN:TBN ratio of at least 0.8, wherein said dispersant is present in an amount of at least 0.1 percent by weight and wherein said dispersant provides at least 0.025 TAN to the lubricant composition.
- the lubricant has a sulfated ash value of up to 1.1 percent.
- the disclosed technology also provides a method for lubricating a mechanical device, comprising supplying thereto the above-described lubricating composition.
- the mechanical device may be an internal combustion engine.
- the disclosed technology further provides a method for improving the retention of TBN in a lubricant employed for lubricating an internal combustion engine, wherein the lubricant may have a sulfated ash value of up to 1.1 percent and comprises (a) an oil of lubricating viscosity and (b) at least one metal- containing detergent in an amount to provide at least 2 TBN to the lubricant; said method comprising including within said lubricant (c) a dispersant comprising an oleophilic portion comprising at least 40 carbon atoms and an acid-bearing portion, characterized in having a TAN:TBN ratio of at least 0.8, wherein said dispersant is present in an amount of at least 0.1 percent by weight and wherein said dispersant provides at least 0.025 TAN to the lubricant composition.
- the disclosed technology further provides for the use of a dispersant comprising an oleophilic portion comprising at least about 40 carbon atoms and an acid-bearing portion, characterized in having a TAN:TBN ratio of at least about 0.8, to improve the TBN retention of a lubricant employed for lubricating an internal combustion engine, wherein said lubricant comprises (a) an oil of lubricating viscosity and (b) at least one metal-containing detergent in an amount to provide at least about 2 TBN to the lubricant; wherein said dispersant is present in an amount of at least about 0.1 percent by weight and wherein said dispersant provides at least about 0.025 TAN to the lubricant composition.
- a dispersant comprising an oleophilic portion comprising at least about 40 carbon atoms and an acid-bearing portion, characterized in having a TAN:TBN ratio of at least about 0.8, to improve the TBN retention of a lubricant employed for lubricating an
- the base oil may be selected from any of the base oils in Groups I-V of the American Petroleum Institute (API) Base Oil Interchangeability Guidelines, namely
- Group I >0.03 and/or ⁇ 90 80 to 120
- PAOs polyalphaolefms
- Groups I, II and III are mineral oil base stocks.
- the oil of lubricating viscosity can include natural or synthetic oils and mixtures thereof. Mixture of mineral oil and synthetic oils, e.g., polyalphaolefin oils and/or polyester oils, may be used.
- Natural oils include animal oils and vegetable oils (e.g. vegetable acid esters) as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Hydrotreated or hydrocracked oils are also useful oils of lubricating viscosity. Oils of lubricating viscosity derived from coal or shale are also useful.
- Synthetic oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins and mixtures thereof, alkylbenzenes, polyphenyl, alkylated diphenyl ethers, and alkylated diphenyl sulfides and their derivatives, analogs and homologues thereof.
- Alkylene oxide polymers and interpolymers and derivatives thereof, and those where terminal hydroxyl groups have been modified by, e.g., esterification or etherification, are other classes of synthetic lubricating oils.
- suitable synthetic lubricating oils comprise esters of dicarboxylic acids and those made from C 5 to C 12 monocar- boxylic acids and polyols or polyol ethers.
- Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, silicon-based oils such as poly-alkyl-, polyaryl-, polyalkoxy-, or polyaryloxy- siloxane oils, and silicate oils.
- oils include those produced by Fischer-Tropsch reactions, typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes.
- oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
- Unrefined, refined, and rerefmed oils either natural or synthetic (as well as mixtures thereof) of the types disclosed hereinabove can used.
- Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
- Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
- Rerefmed oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Rerefmed oils often are additionally processed to remove spent additives and oil breakdown products.
- the lubricants of the disclosed technology will also include at least one metal-containing detergent in an amount to provide at least 2 TBN to the lubricant.
- Metal-containing detergents are typically overbased materials, or overbased detergents, and in one embodiment, the metal-containing detergent comprises an overbased detergent.
- Overbased materials otherwise referred to as overbased or superbased salts, are generally homogeneous Newtonian systems characterized by a metal content in excess of that which would be present for neutralization according to the stoichiometry of the metal and the particular acidic organic com- pound reacted with the metal.
- the overbased materials are prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, such as carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert, organic solvent (e.g., mineral oil, naphtha, toluene, xylene) for said acidic organic material, a stoichiometric excess of a metal base, and a promoter such as a phenol or alcohol and optionally ammonia.
- the acidic organic material will normally have a sufficient number of carbon atoms, for instance, as a hydrocarbyl substituent, to provide a reasonable degree of solubility in oil.
- the amount of excess metal is commonly expressed in terms of metal ratio.
- metal ratio is the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound.
- a neutral metal salt has a metal ratio of one.
- a salt having 4.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5.
- overbased detergents are conventionally prepared using a hydrocarbyl- substituted succinic anhydride, in a small amount, as a processing or manufacturing aid. Accordingly, a small amount of the corresponding metal salt may be present in the overbased detergent as it is commercially supplied. This minor, incidental presence is not to be considered the presence of the dispersant as described herein.
- TBN Total Base Number
- KOH potassium hydroxide
- overbased detergents are commonly provided in a form which contains a certain amount of diluent oil, for example, 40-50% oil, the actual TBN value for such a detergent will depend on the amount of such diluent oil present, irrespective of the "inherent" basicity of the overbased material.
- the TBN of an overbased detergent is to be recalculated to an oil-free basis.
- Detergents which are useful in the present technology may typically have a TBN (oil-free basis) of 100 to 800, and in one embodiment 150 to 750, and in another, 400 to 700. If multiple detergents are employed, the overall TBN of the detergent component (that is, an average of all the specific detergents together) will typically be in the above ranges, and the required contribution to the TBN of the metal-containing detergent component will be the total of the contributions of each individual detergent.
- the overall TBN of the composition will be derived from the TBN contribution of the individual components, such as the dispersant, the detergent, and other basic materials.
- the overall TBN will, in some embodiments, be at least 7 or at least 10, or sometimes even at least 20.
- the amount of TBN provided by the metal-containing detergent will be at least 2 or at least 4 or at least 6, and the amount of the metal containing detergent or detergents will typically be an amount suitable to provide such TBN levels.
- the actual amount of the metal-containing detergent (or detergents) may be 0.2 to 5 percent by weight or 0.3 to 3 percent or 0.5 to 2 percent or 0.9 to 1.5 percent by weight.
- Sulfated ash is another parameter often used to characterize such compositions.
- Certain of the compositions of the present invention can have sulfated ash levels of up to 2.0% (that is, with a lower limit of 0% or 0.05%) or up to 1.8 or to 1.6 or to 1.4%, such as 0.1 to 1.1 % or 0.2 to 1.0% or 0.3 to 0.8% or 0.3 to 0.8% or 0.5 to 0.8%.
- the metal compounds useful in making the basic metal salts are generally any Group 1 or Group 2 metal compounds (CAS version of the Periodic Table of the Elements).
- the Group 1 metals of the metal compound include Group la alkali metals such as sodium, potassium, and lithium, as well as Group lb metals such as copper.
- the Group 1 metals can be sodium, potassium, lithium and copper, and in one embodiment sodium or potassium, and in another embodiment, sodium.
- the Group 2 metals of the metal base include the Group 2a alkaline earth metals such as magnesium, calcium, and barium, as well as the Group 2b metals such as zinc.
- the Group 2 metals are magnesium, calcium, barium, or zinc, and in another embodiments magnesium or calci- um.
- the metal is calcium or sodium or a mixture of calcium and sodium.
- the metal compounds are delivered as metal salts.
- the anionic portion of the salt can be hydroxide, oxide, carbonate, borate, or nitrate.
- Patents describing techniques for making basic salts of sulfonic acids, carboxylic acids, (hydrocarbyl-substituted) phenols, phosphonic acids, and mixtures of any two or more of these include U.S. Patents 2,501 ,731 ; 2,616,905; 2,616,91 1 ;
- the lubricants of the present invention can contain an overbased sulfonate detergent.
- Suitable sulfonic acids include sulfonic and thiosulfonic acids.
- Sulfonic acids include the mono- or polynuclear aromatic or eye lo aliphatic compounds. Oil-soluble sulfonates can be represented for the most
- R -T-(S03-) a and R -(S0 3 -)b where T is a cyclic nucleus such as typically benzene or toluene; R is an aliphatic group such as alkyl, alkenyl, alkoxy, or alkoxyalkyl; (R )-T typically contains a total of at least 15 carbon atoms; and R is an aliphatic hydrocarbyl group typically contain- ing at least 15 carbon atoms. Examples of R are alkyl, alkenyl, alkoxyalkyl, and
- sulfonate detergent may be a predominantly linear alkylbenzenesulfonate detergent having a metal ratio of at least 8 as described in paragraphs [0026] to [0037] of US Patent Application 2005/065045.
- the linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often in the 2, 3 or 4 position of the linear chain, and in some instances predominantly in the 2 position.
- R 1 is an aliphatic hydrocarbyl group of 4 to 400 carbon atoms, or 6 to 80 or 6 to 30 or 8 to 25 or 8 to 15 carbon atoms
- Ar is an aromatic group (which can be a benzene group or another aromatic group such as toluene or naphthalene)
- a and b are independently numbers of at least one, the sum of a and b being in the range of two up to the number of displaceable hydrogens on the aromatic nucleus or nuclei of Ar.
- a and b are independently numbers in the range of 1 to 4, or 1 to 2.
- R 1 and a are typically such that there is an average of at least 8 aliphatic carbon atoms provided by the R 1 groups for each phenol compound.
- Phenate detergents are also sometimes provided as sulfur-bridged species.
- the metal-containing detergent comprises a calcium phenate detergent.
- the calcium phenate detergent is not overbased, that is, it may contain a substantially stoichiometric amount of metal. Such non-overbased phenate detergents are still typically basic in character (perhaps because of the relatively weakly acidic character of the phenol substrate) and thus will still typically contribute TBN to a lubricant.
- the metal-containing detergent comprises an overbased calcium sulfonate, an overbased calcium phenate, or mixtures thereof.
- the overbased material is an overbased saligenin detergent.
- Overbased saligenin detergents are commonly overbased magnesium salts which are based on saligenin derivatives.
- a general example of such a saligenin derivative can be represented by the formula
- X comprises -CHO or -CH 2 OH
- Y comprises -CH 2 - or -CH 2 OCH 2 -
- -CHO groups typically comprise at least 10 mole percent of the X and Y groups
- M is hydrogen, ammonium, or a valence of a metal ion (that is to say, in the case of a multivalent metal ion, one of the valences is satisfied by the illustrated structure and other valences are satisfied by other species such as anions, or by another instance of the same structure)
- Ri is a hydrocarbyl group containing 1 to 60 carbon atoms
- m is 0 to typically 10
- each p is independently 0, 1 , 2, or 3, provided that at least one aromatic ring contains an R 1 substituent and that the total number of carbon atoms in all R 1 groups is at least 7.
- one of the X groups can be hydrogen.
- M is a valence of a Mg ion or a mixture of Mg and hydrogen.
- Other metals include alkali metals such as lithium, sodium, or potassium; alkaline earth metals such as calcium or barium; and other metals such as copper, zinc, and tin.
- the expression "represented by the formula” indicates that the formula presented is generally representative of the structure of the chemical in question. However, it is well known that minor variations can occur, including in particular positional isomerization, that is, location of the X, Y, and R groups at different position on the aromatic ring from those shown in the structure.
- Saligenin detergents are disclosed in greater detail in U.S. Patent 6,310,009, with special reference to their methods of synthesis (Column 8 and Example 1) and preferred amounts of the various species of X and Y (Column 6).
- Salixarate detergents are overbased materials that can be represented by a substantially linear (as opposed to macrocylcic) compound comprising at least one unit of formula (I) or formula (II):
- R is hydrogen or a hydrocarbyl group or a valence of a metal ion;
- R is hydroxyl or a hydrocarbyl group and j is 0, 1 , or 2;
- R 6 is hydrogen, a hydrocarbyl group, or a hetero- substituted hydrocarbyl group; either R 4 is hydroxyl and R 5 and R 7 are independently either hydrogen, a hydrocarbyl group, or hetero-substituted hydrocarbyl group, or else R 5 and R 7 are both hydroxyl and R 4 is hydrogen, a hydrocarbyl group, or a hetero-substituted hydrocarbyl group; provided that at least one of R 4 , R 5 , R 6 and R 7 is hydrocarbyl containing at least 8 carbon atoms; and wherein the molecules on average contain at least one of unit (I) or (III) and at least one of unit (
- salixarate derivatives have a predominantly linear, rather than macrocyclic, structure, although both structures are intended to be encompassed by the term "salixarate.”
- Glyoxylate detergents are similar overbased materials which are based on an anionic group which, in one embodiment, may have the structure
- each R is independently an alkyl group containing at least 4, and in certain embodiments at least 8 carbon atoms, provided that the total number of carbon atoms in all such R groups is at least 12, or at least 16 or 24.
- each R can be an olefin polymer substituent.
- the acidic material upon from which the overbased glyoxylate detergent is prepared is the condensation product of a hydroxyaromatic material such as a hydrocarbyl-substituted phenol with a carboxylic reactant such as glyoxylic acid and other omega-oxoalkanoic acids.
- a hydroxyaromatic material such as a hydrocarbyl-substituted phenol
- carboxylic reactant such as glyoxylic acid and other omega-oxoalkanoic acids.
- the overbased detergent can also be an overbased salicylate which may be an alkali metal salt or an alkaline earth metal salt of an alkylsalicylic acid.
- the salicylic acids may be hydrocarbyl-substituted salicylic acids wherein each substituent contains an average of at least 8 carbon atoms per substituent and 1 to 3 substituents per molecule.
- the substituents can be polyalkene substituents, where polyalkenes include homopolymers and interpolymers of polymerizable olefin monomers of 2 to 16, or 2 to 6, or 2 to 4 carbon atoms.
- the olefins may be monoolefms such as ethylene, propylene, 1-butene, isobutene, and 1-octene; or a polyolefinic monomer, such as diolefmic monomer, such 1 ,3-butadiene and isoprene.
- the hydrocarbyl substituent group or groups on the salicylic acid contains 7 to 300 carbon atoms and can be an alkyl group having a molecular weight of 150 to 2000.
- the polyalkenes and polyalkyl groups are prepared by conventional procedures, and substitution of such groups onto sali- cylic acid can be effected by known methods.
- Alkyl salicylates may be prepared from an alkylphenol by Kolbe-Schmitt reaction; alternatively, calcium salicylate can be produced by direct neutralization of alkylphenol and subsequent carbona- tion.
- Overbased salicylate detergents and their methods of preparation are disclosed in U.S. Patents 4,719,023 and 3,372,1 16.
- overbased detergents can include overbased detergents having a Mannich base structure, as disclosed in U.S. Patent 6,569,818.
- the hydrocarbyl substituents on hydroxy- substituted aromatic rings in the above detergents are free of or substantially free of C 12 aliphat- ic hydrocarbyl groups (e.g., less than 1%, 0.1%, or 0.01% by weight of the substituents are C 12 aliphatic hydrocarbyl groups).
- such hydrocarbyl substituents contain at least 14 or at least 18 carbon atoms.
- Another component of the disclosed technology is a dispersant.
- Dispersants generally, are well known in the field of lubricants and include primarily what is known as ashless dispersants and polymeric dispersants.
- Ashless dispersants are so-called because, as supplied, they do not contain metal and thus do not normally contribute to sulfated ash when added to a lubricant. However they may, of course, interact with ambient metals once they are added to a lubricant which includes metal-containing species.
- Ashless dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides, having a variety of chemical structures including typically
- each R is independently an alkyl group, frequently a polyisobutylene group with a molecular weight (M n ) of 500-5000 based on the polyisobutylene
- R are alkylene groups, commonly ethylene (C 2 H 4 ) groups.
- alkylene groups commonly ethylene (C 2 H 4 ) groups.
- Such molecules are commonly derived from reaction of an alkenyl acylating agent with a polyamine, and a wide variety of linkages between the two moieties is possible beside the simple imide structure shown above, including a variety of amides and quaternary ammonium salts.
- the amine portion is shown as an alkylene polyamine, although other aliphatic and aromatic mono- and polyam- ines may also be used.
- modes of linkage of the R 1 groups onto the imide structure are possible, including various cyclic linkages.
- the ratio of the carbonyl groups of the acylating agent to the nitrogen atoms of the amine may be 1 :0.5 to 1 :3, and in other instances 1 : 1 to 1 :2.75 or 1 : 1.5 to 1 :2.5.
- Succinimide dispersants are more fully described in U.S. Patents 4,234,435 and 3,172,892 and in EP 0355895.
- the dispersant is prepared by a process that involves the presence of small amounts of chlorine or other halogen, as described in U.S. Patent 7,615,521 , see, e.g., col. 4 and preparative example A.
- Such dispersants typically have some carbocyclic structures in the attachment of the hydrocarbyl substituent to the acidic or ami die “head” group.
- the dispersant is prepared by a thermal process involving an "ene” reaction, without the use of any chlorine or other halogen, as described in U.S. Patent 7,615,521. See col. 4, bottom, col. 5, and preparative example B.
- Such disper- sants typically do not contain the above-described carbocyclic structures at the point of attachment.
- Another class of ashless dispersant is high molecular weight esters. These materials are similar to the above-described succinimides except that they may be seen as having been prepared by reaction of a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol such as glycerol, pentaerythritol, or sorbitol. Such materials are described in more detail in U.S. Patent 3,381,022.
- a succinic-based dispersant may be formed by reacting maleic anhydride or a reactive equivalent thereof, such as an acid or ester, with a hydrocarbon chain by any method such as those disclosed above (e.g., chlorine-based process or thermal process).
- Other acids or equivalents thereof may be used in place of the maleic anhydride; these include fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citaconic anhydride, and cinnamic acid as well as other ethylenically unsaturated acids such as acrylic or methacrylic acid; and their reactive equivalents.
- Mannich bases are materials which are formed by the condensation of a higher molecular weight, alkyl substituted phenol, an alkylene polyamine, and an aldehyde such as formaldehyde. Such materials may have the general structure
- dispersants include polymeric dispersant additives, which are generally hydrocarbon-based polymers which contain polar functionality to impart dispersancy characteristics to the polymer.
- Dispersants can also be post -treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in U.S. Patent 4,654,403.
- the dispersants of the disclosed technology are those which comprise an oleophilic portion comprising at least 40 carbon atoms and an acid-bearing portion.
- the acid-bearing portion is typically a part of or associated with the polar "head" portion of the dispersant.
- dispersants may contain reacted/condensed acidic functionality, there will be at least some acidic functionality that is not converted to a non-acidic form such as an amide, imide, or ester.
- the dispersant may, in one embodiment, comprise a polyolefm-substituted succinic acid, ester, amide, or imide, provided the dispersant contains at least some acid functionality.
- the acid functionality may be measured as total acid number (TAN, ASTM D 974) and will typically be an amount to impart a TAN to the dispersant of at least 3, or at least 5 or 10 or 20 or 40 (expressed on an oil-free basis).
- the TAN of the dispersant may be up to 200 or 150 or 100.
- a dispersant having acid functionality may be provided in the acid form, or it may be provided in a salt form, neutralized, for instance, with a Group I or Group II metal (e.g., an alkali or alkaline earth metal). Such neutralization may (temporarily) reduce or eliminate the measurable TAN.
- a Group I or Group II metal e.g., an alkali or alkaline earth metal.
- Such neutralization may (temporarily) reduce or eliminate the measurable TAN.
- metal salts are to be considered as acid-containing dispersants, and their TAN is to be regarded as that of their unneutralized form.
- the unneutralized form may be regenerated, if desired, by treatment of the salt with an acid.
- dispersants may contain anhydride functionality in place of the corresponding acid functionality.
- anhydride groups are typically hydrolyzed and titrate as TAN, so anhydride-containing dispersants are likewise to be considered as acid-containing dispersants.
- the dispersant may also exhibit basicity, as measured by TBN. This will particularly be the case if the dispersant is prepared with an amine, such as a polyamine, and the amine contains one or more amino groups that have not reacted with acidic groups of the dispersant.
- the TBN of the dispersant may be 1 to 50, or to 40 or to 20 or to 10.
- the dispersant may not exhibit basicity (that is, have a TBN of 0 or nearly 0).
- the dispersant has a TBN of zero. Such could be the case if no amine nitrogen is present on the dispersant.
- An example of a non- basic dispersant would be a long-chain hydrocarbyl-substituted succinic acid.
- the dispersants of the disclosed technology are characterized by having a TAN:TBN ratio of at least 0.8: 1 (that is, at least 0.8), and in certain embodiments a TAN:TBN ratio of at least 1 or 2 or 5 or 10 or 12.
- the ratio will be considered to be at least as large as any of the above-mentioned numbers.
- Such dispersants may be referred to herein as a "high TAN:TBN dispersant” or "the dispersant having a TAN:TBN ratio of at least 0.8" or at least any other such number.
- the presence of a dispersant with any of these (generally large) TAN:TBN ratios tends to promote the retention of TBN of the metal-containing detergent, upon use in a lubricating application such as an engine lubricant.
- the amount of the high TAN:TBN dispersant may be an amount of at least 0.1% of the lubricant composition, or at least 0.3% or 0.5%, and in certain embodiments at most 4% or 3% or 2% or 1.5% by weight. In certain embodiments the amount of the high TAN:TBN dispersant may be the amount to provide at least 0.025 TAN or 0.1 TAN to the lubricant composition, and in certain embodiments up to 1.0 or 0.5 TAN. Other amounts may be readily calculated from the above percentage amounts and the TAN of the particular dispersant.
- the lubricant may also contain one or more dispersants having a TAN:TBN ratio of less than 0.8, in conventional amounts.
- the entire dispersant component e.g., mixture of different components
- the TAN:TBN ratio of all the dispersants in the lubricant, taken together is at least 0.8.
- the lubricant may further contain conventional amounts of other components that are useful for the desired end use, e.g., for an engine lubricant.
- additional components include antioxidants, friction modifiers, anti-wear agents, viscosity modifiers, and pour point depressants. These may be used individually or in combination.
- Antioxidants encompass phenolic antioxidants, which may comprise a butyl substituted phenol containing 2 or 3 t-butyl groups. The para position may also be occupied by a hydrocarbyl group, an ester-containing group, or a group bridging two aromatic rings. The latter antioxidants are described in greater detail in U.S. Patent 6,559,105.
- Antioxidants also include aromatic amines such as nonylated diphenyl amines or alkylated phenylnaphthyl amine.
- Other antioxidants include sulfurized olefins, titanium compounds, and molybdenum compounds.
- U.S. Pat. No. 4,285,822 discloses lubricating oil compositions containing a molybdenum and sulfur containing composition.
- U.S. Patent Application Publication 2006-0217271 discloses a variety of titanium compounds, including titanium alkoxides and titanated dispersants, which materials may also impart improvements in deposit control and filterability.
- Other titanium compounds include titanium carboxylates such as neodecanoate.
- antioxidants will, of course, depend on the specific antioxidant and its individual effectiveness, but illustrative total amounts can be 0.01 to 5 percent by weight or 0.15 to 4.5 percent or 0.2 to 4 percent. Additionally, more than one antioxidant may be present, and certain combinations of these can be synergistic in their combined overall effect.
- Friction modifiers are well known to those skilled in the art.
- a list of friction modifiers that may be used is included in U.S. Patents 4,792,410, 5,395,539, 5,484,543 and 6,660,695.
- U.S. Patent 5, 110,488 discloses metal salts of fatty acids and especially zinc salts, useful as friction modifiers.
- a list of supplemental friction modifiers that may be used may include:
- antiwear agent Another additive is an antiwear agent.
- anti-wear agents include phosphorus-containing antiwear/extreme pressure agents such as metal thiophosphates, phosphoric acid esters and salts thereof, phosphorus-containing carboxylic acids, esters, ethers, and amides; and phosphites.
- a phosphorus antiwear agent may be present in an amount to deliver 0.01 to 0.2 or 0.015 to 0.15 or 0.02 to 0.1 or 0.025 to 0.08 percent phosphorus.
- the antiwear agent is a zinc dialkyl dithiophosphate (ZDP).
- ZDP zinc dialkyl dithiophosphate
- suitable amounts may include 0.09 to 0.82 percent.
- Non-phosphorus-containing anti-wear agents include borate esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins.
- antiwear agents include tartrate esters, tartramides, and tartrimides, such as oleyl tartrimide, as well as esters, amides, and imides of hydroxy-polycarboxylic acids in general. These materials may also impart additional functionality to a lubricant beyond antiwear performance, sometimes or especially in the presence of some ZDP. These materials are described in greater detail in US Publication 2006-0079413 and PCT publication WO2010/077630.
- Viscosity modifiers VM
- DVM dispersant viscosity modifiers
- VMs and DVMs may include polymethacrylates, polyacrylates, polyolefins, hydrogenated vinyl aromatic-diene copolymers (e.g., styrene- butadiene, styrene-isoprene), styrene-maleic ester copolymers, and similar polymeric substances including homopolymers, copolymers, and graft copolymers.
- the DVM may comprise a nitrogen-containing methacrylate polymer, for example, a nitrogen-containing methacrylate polymer derived from methyl methacrylate and dimethyl aminopropyl amine.
- Examples of commercially available VMs, DVMs and their chemical types may include the following: polyisobutylenes (such as IndopolTM from BP Amoco or ParapolTM from ExxonMobil); olefin copolymers (such as LubrizolTM 7060, 7065, and 7067 from Lubrizol and LucantTM HC-2000L and HC-600 from Mitsui); hydrogenated styrene-diene copolymers (such as ShellvisTM 40 and 50, from Shell and LZ® 7308, and 7318 from Lubrizol); styrene/maleate copolymers, which are dispersant copolymers (such as LZ® 3702 and 3715 from Lubrizol); polymethacrylates, some of which have dispersant properties (such as those in the ViscoplexTM series from RohMax, the HitecTM series of viscosity index improvers from Afton, and LZ® 7702, LZ® 7727, LZ®
- Viscosity modifiers that may be used are described in U.S. patents 5,157,088, 5,256,752 and 5,395,539.
- the VMs and/or DVMs may be used in the functional fluid at a concentration of up to 20% by weight. Concentrations of 1 to 12%, or 3 to 10%> by weight may be used.
- Pour point depressants may include alkylphenols and derivatives thereof, or ethylene vinyl acetate copolymers, and mixtures thereof.
- additives that may optionally be used in lubricating oils include extreme pressure agents, color stabilizers and anti-foam agents.
- the lubricants described herein may be used for the lubrication of mechanical devices, especially those mechanical devices, such as internal combustion engines, for which the presence and retention of basicity (TBN) is desirable.
- Such engines include those fueled by gasoline, diesel fuel, alcohol, gasoline- alcohol mixtures, and biodiesel fuels.
- the lubricant is often supplied from a sump.
- the lubricant may be supplied from a storage vessel.
- the amount of each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated.
- each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
- hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
- hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the con- text of this invention, do not alter the predominantly hydrocarbon nature of the substituent; and hetero substituents, that is, substituents which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain.
- TBN neutralization/ retention is determined by a stopped-flow neutralization test. This test uses a technique called stopped-flow kinetics, which rapidly mixes an acid-containing solution (or mixture) with a secondary solution, in this case, containing the mixture of detergent and dispersant to be tested.
- the detergent/dispersant solution is made by diluting the corresponding concentrated additives in a hydrocarbon solvent. The dilution range, or concentration, is chosen to give a suitable total reaction time, typically between 0.1 and 5 seconds.
- the acid-containing solution is a dispersion of aqueous sulfuric acid droplets in the same hydrocarbon solvent.
- the concentration of sulfuric acid within the aqueous phase is 0.05 M.
- a water-soluble pH-sensitive dye is also added to the dispersed aqueous phase.
- the spectrometer monitors the color and color change of the dye over a few seconds (typically about 10 seconds) as the basic detergent neutralizes the sulfuric acid.
- a rate constant is thereby determined from the rate of color change, and rate constants are determined over a range of TBN values.
- the overall rate of acid neutralization (that is, the rate constant per unit of TBN) is determined from the gradient of the relationship between TBN and rate constant, with units of s ⁇ TBN "1 .
- the amount of dispersant is about 2x the amount of detergent. (The neutralization rate numbers are not corrected for the amount of diluent oil present, but the TAN and TBN values for the dispersants are corrected.)
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US201161443792P | 2011-02-17 | 2011-02-17 | |
PCT/US2012/025203 WO2012112658A1 (en) | 2011-02-17 | 2012-02-15 | Lubricants with good tbn retention |
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EP2675876A1 true EP2675876A1 (de) | 2013-12-25 |
EP2675876B1 EP2675876B1 (de) | 2016-12-14 |
EP2675876B2 EP2675876B2 (de) | 2024-07-24 |
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US (1) | US9528068B2 (de) |
EP (1) | EP2675876B2 (de) |
JP (1) | JP5840233B2 (de) |
CN (1) | CN103476910B (de) |
CA (1) | CA2827438A1 (de) |
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US8513169B2 (en) | 2006-07-18 | 2013-08-20 | Infineum International Limited | Lubricating oil compositions |
EP1884557B1 (de) | 2006-07-20 | 2021-03-31 | Infineum International Limited | Schmierölzusammensetzung |
US11168280B2 (en) * | 2015-10-05 | 2021-11-09 | Infineum International Limited | Additive concentrates for the formulation of lubricating oil compositions |
Family Cites Families (80)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2501731A (en) | 1946-10-14 | 1950-03-28 | Union Oil Co | Modified lubricating oil |
US2616911A (en) | 1951-03-16 | 1952-11-04 | Lubrizol Corp | Organic alkaline earth metal complexes formed by use of sulfonic promoters |
US2616925A (en) | 1951-03-16 | 1952-11-04 | Lubrizol Corp | Organic alkaline earth metal complexes formed by use of thiophosphoric promoters |
US2616905A (en) | 1952-03-13 | 1952-11-04 | Lubrizol Corp | Organic alkaline earth metal complexes and methods of making same |
US2777874A (en) | 1952-11-03 | 1957-01-15 | Lubrizol Corp | Metal complexes and methods of making same |
DE1248643B (de) | 1959-03-30 | 1967-08-31 | The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) | Verfahren zur Herstellung von öllöslichen aeylierten Aminen |
US3488284A (en) | 1959-12-10 | 1970-01-06 | Lubrizol Corp | Organic metal compositions and methods of preparing same |
BE637123A (de) | 1962-09-07 | |||
US3282835A (en) | 1963-02-12 | 1966-11-01 | Lubrizol Corp | Carbonated bright stock sulfonates and lubricants containing them |
US3381022A (en) | 1963-04-23 | 1968-04-30 | Lubrizol Corp | Polymerized olefin substituted succinic acid esters |
US3320162A (en) | 1964-05-22 | 1967-05-16 | Phillips Petroleum Co | Increasing the base number of calcium petroleum sulfonate |
US3318809A (en) | 1965-07-13 | 1967-05-09 | Bray Oil Co | Counter current carbonation process |
GB1105217A (en) | 1965-10-05 | 1968-03-06 | Lubrizol Corp | Process for preparing basic metal phenates |
US3365396A (en) | 1965-12-28 | 1968-01-23 | Texaco Inc | Overbased calcium sulfonate |
US3384585A (en) | 1966-08-29 | 1968-05-21 | Phillips Petroleum Co | Overbasing lube oil additives |
US3634515A (en) | 1968-11-08 | 1972-01-11 | Standard Oil Co | Alkylene polyamide formaldehyde |
US3629109A (en) | 1968-12-19 | 1971-12-21 | Lubrizol Corp | Basic magnesium salts processes and lubricants and fuels containing the same |
US3714042A (en) | 1969-03-27 | 1973-01-30 | Lubrizol Corp | Treated overbased complexes |
US4234435A (en) | 1979-02-23 | 1980-11-18 | The Lubrizol Corporation | Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation |
US4285822A (en) | 1979-06-28 | 1981-08-25 | Chevron Research Company | Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing the composition |
US4375418A (en) | 1981-10-28 | 1983-03-01 | Texaco Inc. | Lubricating oil composition |
JPH07103390B2 (ja) | 1982-05-14 | 1995-11-08 | エクソン リサーチ アンド エンヂニアリング コムパニー | 潤滑油添加剤 |
US4554086A (en) | 1984-04-26 | 1985-11-19 | Texaco Inc. | Borate esters of hydrocarbyl-substituted mono- and bis-succinimides containing polyamine chain linked hydroxyacyl groups and lubricating oil compositions containing same |
US4594378A (en) | 1985-03-25 | 1986-06-10 | The Lubrizol Corporation | Polymeric compositions, oil compositions containing said polymeric compositions, transmission fluids and hydraulic fluids |
GB8531626D0 (en) | 1985-12-23 | 1986-02-05 | Shell Int Research | Grease composition |
US5110488A (en) | 1986-11-24 | 1992-05-05 | The Lubrizol Corporation | Lubricating compositions containing reduced levels of phosphorus |
GB8628609D0 (en) | 1986-11-29 | 1987-01-07 | Bp Chemicals Additives | Lubricating oil additives |
US4792410A (en) | 1986-12-22 | 1988-12-20 | The Lubrizol Corporation | Lubricant composition suitable for manual transmission fluids |
IN172215B (de) | 1987-03-25 | 1993-05-08 | Lubrizol Corp | |
US5157088A (en) | 1987-11-19 | 1992-10-20 | Dishong Dennis M | Nitrogen-containing esters of carboxy-containing interpolymers |
GB8818711D0 (en) * | 1988-08-05 | 1988-09-07 | Shell Int Research | Lubricating oil dispersants |
US4857214A (en) | 1988-09-16 | 1989-08-15 | Ethylk Petroleum Additives, Inc. | Oil-soluble phosphorus antiwear additives for lubricants |
WO1990004625A2 (en) | 1988-10-24 | 1990-05-03 | Exxon Chemical Company | Amide containing friction modifier for use in power transmission fluids |
US5075383A (en) | 1990-04-11 | 1991-12-24 | Texaco Inc. | Dispersant and antioxidant additive and lubricating oil composition containing same |
US5089156A (en) | 1990-10-10 | 1992-02-18 | Ethyl Petroleum Additives, Inc. | Ashless or low-ash synthetic base compositions and additives therefor |
JP3040618B2 (ja) | 1992-11-20 | 2000-05-15 | コスモ石油株式会社 | 新規ビスカスカップリング用流体組成物 |
US5356552A (en) | 1993-03-09 | 1994-10-18 | Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. | Chlorine-free lubricating oils having modified high molecular weight succinimides |
GB2284815B (en) | 1993-12-14 | 1997-09-10 | Ethyl Petroleum Additives Ltd | Dispersants for lubricating oil |
US6310011B1 (en) | 1994-10-17 | 2001-10-30 | The Lubrizol Corporation | Overbased metal salts useful as additives for fuels and lubricants |
GB9511266D0 (en) | 1995-06-05 | 1995-08-02 | Exxon Chemical Patents Inc | Ester-free synthetic lubricating oils |
JP3504405B2 (ja) | 1995-10-23 | 2004-03-08 | 新日本石油株式会社 | ディーゼルエンジン油組成物 |
US5925151A (en) | 1996-09-19 | 1999-07-20 | Texaco Inc | Detergent additive compositions for diesel fuels |
WO1999025677A1 (en) | 1997-11-13 | 1999-05-27 | Lubrizol Adibis Holdings (Uk) Limited | Salicyclic calixarenes and their use as lubricant additives |
JP2001158896A (ja) | 1999-12-02 | 2001-06-12 | Chevron Oronite Ltd | ガスエンジンの潤滑に特に有効な内燃機関用潤滑油組成物 |
EP1254100A1 (de) | 2000-02-07 | 2002-11-06 | Bp Oil International Limited | Calixarene und ihre verwendung als schmierstoffadditive |
US6559105B2 (en) | 2000-04-03 | 2003-05-06 | The Lubrizol Corporation | Lubricant compositions containing ester-substituted hindered phenol antioxidants |
US6310009B1 (en) | 2000-04-03 | 2001-10-30 | The Lubrizol Corporation | Lubricating oil compositions containing saligenin derivatives |
US6569818B2 (en) | 2000-06-02 | 2003-05-27 | Chevron Oronite Company, Llc | Lubricating oil composition |
EP1213341A1 (de) | 2000-12-07 | 2002-06-12 | Infineum International Limited | Schmierölzusammensetztungen |
WO2002102942A2 (en) | 2001-02-14 | 2002-12-27 | The Lubrizol Corporation | Fuel additive composition and fuel composition and method thereof |
WO2003033629A1 (fr) | 2001-10-12 | 2003-04-24 | Nippon Oil Corporation | Composition d'huile de lubrification pour moteur thermique |
WO2003040273A2 (en) | 2001-11-05 | 2003-05-15 | The Lubrizol Corporation | Lubricating composition with improved fuel economy |
US6500786B1 (en) | 2001-11-26 | 2002-12-31 | Infineum International Ltd. | Lubricating oil composition |
US6660695B2 (en) | 2002-03-15 | 2003-12-09 | Infineum International Ltd. | Power transmission fluids of improved anti-shudder properties |
JP4017514B2 (ja) | 2002-12-27 | 2007-12-05 | コスモ石油ルブリカンツ株式会社 | エンジン油 |
EP1585773A1 (de) | 2003-01-21 | 2005-10-19 | The Lubrizol Corporation | Schwach gefärbte, von polyisobutylenbernsteinsäureanhydrid abgeleitete emulgatoren |
CA2535107A1 (en) * | 2003-08-01 | 2005-02-10 | The Lubrizol Corporation | Mixed dispersants for lubricants |
WO2005037967A1 (ja) | 2003-10-16 | 2005-04-28 | Nippon Oil Corporation | 潤滑油添加剤及び潤滑油組成物 |
US7407918B2 (en) | 2003-12-11 | 2008-08-05 | Afton Chemical Corporation | Lubricating oil compositions |
AU2004303846B2 (en) * | 2003-12-12 | 2009-10-29 | The Lubrizol Corporation | Lubricating composition containing metal salixarate as detergent |
EP1642956A1 (de) | 2004-06-11 | 2006-04-05 | Infineum International Limited | Zusatzstoffkombination als Detergens für Schmierölzusammensetzungen |
JP2008505995A (ja) * | 2004-07-09 | 2008-02-28 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | 潤滑油組成物 |
US20060030498A1 (en) | 2004-08-05 | 2006-02-09 | Hartley Rolfe J | Lubricating oil additive concentrates |
US7651987B2 (en) | 2004-10-12 | 2010-01-26 | The Lubrizol Corporation | Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof |
EP1803799A4 (de) | 2004-10-19 | 2012-09-05 | Nippon Oil Corp | Schmierstoffzusammensetzung und antioxidanszusammensetzung |
EP1816182B1 (de) | 2004-11-24 | 2010-09-15 | Nippon Oil Corporation | Schmierölzusammensetzung |
JP4806528B2 (ja) | 2004-12-22 | 2011-11-02 | 出光興産株式会社 | 内燃機関用潤滑油組成物 |
JP5198719B2 (ja) | 2004-12-28 | 2013-05-15 | シェブロンジャパン株式会社 | 潤滑油組成物 |
EP1877526B1 (de) | 2005-03-28 | 2015-05-13 | The Lubrizol Corporation | Titanverbindungen und -komplexe als additive in schmiermitteln |
US7772171B2 (en) | 2006-07-17 | 2010-08-10 | The Lubrizol Corporation | Method of lubricating an internal combustion engine and improving the efficiency of the emissions control system of the engine |
US9012382B2 (en) * | 2006-07-19 | 2015-04-21 | Infineum International Limited | Lubricating oil composition |
US20090305924A1 (en) | 2006-08-07 | 2009-12-10 | Alexandra Mayhew | Method of Lubricating an Internal Combustion Engine |
US8026199B2 (en) | 2006-11-10 | 2011-09-27 | Nippon Oil Corporation | Lubricating oil composition |
US20080146473A1 (en) | 2006-12-19 | 2008-06-19 | Chevron Oronite Company Llc | Lubricating oil with enhanced piston cleanliness control |
EP2141220B1 (de) | 2007-03-28 | 2016-12-21 | Idemitsu Kosan Co., Ltd. | Schmiermittelzusammensetzung |
KR101496484B1 (ko) | 2007-05-24 | 2015-03-09 | 더루우브리졸코오포레이션 | 하이드록시폴리카르복시산 유도체 및 몰리브덴 화합물을 기반으로 하는 무회분 내마모제를 함유하는 윤활 조성물 |
WO2009085800A1 (en) * | 2007-12-27 | 2009-07-09 | The Lubrizol Corporation | Lubricating composition containing detergent |
CN102224228A (zh) | 2008-07-16 | 2011-10-19 | 卢布里佐尔公司 | 用于天然气发动机的改进的润滑剂 |
CN102307976A (zh) | 2008-12-09 | 2012-01-04 | 卢布里佐尔公司 | 含衍生自羟基羧酸的化合物的润滑组合物 |
CN102365353A (zh) * | 2009-04-07 | 2012-02-29 | 英菲诺姆国际有限公司 | 船舶发动机润滑 |
-
2012
- 2012-02-15 US US13/984,288 patent/US9528068B2/en active Active
- 2012-02-15 EP EP12705222.3A patent/EP2675876B2/de active Active
- 2012-02-15 JP JP2013554568A patent/JP5840233B2/ja active Active
- 2012-02-15 WO PCT/US2012/025203 patent/WO2012112658A1/en active Application Filing
- 2012-02-15 CA CA2827438A patent/CA2827438A1/en not_active Abandoned
- 2012-02-15 CN CN201280018705.5A patent/CN103476910B/zh active Active
- 2012-02-15 SG SG2013061072A patent/SG192724A1/en unknown
Non-Patent Citations (1)
Title |
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See references of WO2012112658A1 * |
Also Published As
Publication number | Publication date |
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CN103476910B (zh) | 2017-08-08 |
WO2012112658A8 (en) | 2012-11-08 |
SG192724A1 (en) | 2013-09-30 |
US9528068B2 (en) | 2016-12-27 |
CA2827438A1 (en) | 2012-08-23 |
EP2675876B1 (de) | 2016-12-14 |
JP5840233B2 (ja) | 2016-01-06 |
CN103476910A (zh) | 2013-12-25 |
US20150045268A1 (en) | 2015-02-12 |
EP2675876B2 (de) | 2024-07-24 |
JP2014505781A (ja) | 2014-03-06 |
WO2012112658A1 (en) | 2012-08-23 |
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